Process for the production of



Le'o E. Rademac'her,

'with aniline in aqueous medium i to'the "free -base.

- mer 'the monomer of its high color.

rno'cuss FOR THE *PRODUCTION or MONOBHENYLMELAMINE Longmeadow, Mass, 'assigrior to Monsanto Chemical Company, .'St. Louis, Mo., a corporation'ofDelaware No Drawing. Application August 8, 1956 Serial No. 602,927 3 Claims. (or. 260-2496) The present invention relates to monophenylmelamine production. Monophenylmelamine (2-ariilino 4,6 diamino-s-triazine) is useful as an aminoplast in the preparation of surface coating resins and as an intermediate in the preparation of various other types of synthetic resins. It is well known that monophenylmelarnine can be prepared by the reaction of 2,4-diamino-6-chloro-s-triazine followed by neutralization to convert the monophenylmelamine hydrochloride This method is generally satisfactory. However, it has been observed that when the monophenylmelamine so produced is resinified by reaction with formaldehyde, for example, the resulting resin is characterized by an undesirable color ranging from pin iorilavenderto dark brown which makes it unsuitable in many common applications. Frequently, the color may be ,visually observed inthe monophenylmelamine monodiscoloration is not readily apparent to the naked eye, color bodies are present in which are so intensified in the resinfication process that the resulting resin is unacceptable 'because discovered that monophenylmelamine suitable for preparing resins of a satisfactory color and for other uses in color of the final product is important can be prepared and used without additional purification if certain modifications are made in the process as practiced in the prior art. Briefly, this invention involves the use of a protective inert atmosphere during the reaction to prevent the'formation of the substance or substances which are responsible for the objectionable color in the substituted melamine.

According to a specific embodiment the 2,4-diamino-6-chloro-s-triazine, water, and aniline are slurried together and heated to 95-l05 C. under a protective atmosphere of nitrogen or some other inert gas. The reaction mixture is maintained in this temperature range for 0.5 to 4.0 hours under the inert atmosphere and then filtered while hot, cooled to 25-35" C., and neutralized with a strong base. The precipitated monophenylmelamine is recovered by filtration and thoroughly washed with water. It is then ready for use or may be dried if desired.

The invention is of the invention,

illustrated by the following examples in which all parts given are by weight. However, these are not to be construed as limiting in any manner except as it is limited in the appended claims.

Example 1 A one-liter, three-necked flask was fitted with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube of suflicient length so as to extend about /2 inch below the surface of the liquid. Four hundred parts of water, 50.0 parts (0.344 mole) of 2,4-diamino-6-chloro-s-triazine and 32.88 parts (0.353 mole) of aniline were charged to the flask. Dry nitrogen was passed into the Uniw Stat s .P to 3 at atmospheric pressure to an endpoint temperature of ,n-b'u'tanol (1.33 moles),

;:equipped with a stirrer,

- 10% "aqueous oxalic acid.

i 2,861,070 fiatented Nov- ,1- 1 958 2 A v liters per hour. The mixture was heated to reflux temperature over a 35-minute period and maintained under reflux conditions for about 3 hours. The solution was filtered while hot and the filtrate was cooled to 30 C. While the filtrate solution was stirred vigorously, a 5% aqueous solution of sodium hydroxide was slowly added to it until the pH rose to 10.4. This required 270 ml. of sodium hydroxide. The monophenylmelamine precipitated was filtered off and washed by slur'ryingit first with 500 ml. of 1% aqueous sodium hydroxide, draining, and reslurrying with 500 ml. of water. The white product was then dried at C. for 18 hours to yield 63.0 parts (90.7%) of the dry material. This monophenylmelarnine was used in formulating a surface coating resin'as follows:

Approximately 50 parts of the monophenylmelamine (0.25 mole), 101 parts of a 37% aqueous formaldehyde solution (1.25 moles of formaldehyde), 100 parts of and 50 parts of water (28 500 ml., 3-necked Pyrex flask a thermometer, and ,a reflux Enough of a 5%"aqueous solution of sodium was added to produce a pH of 8.5-9.0 and 'the mixture was heated while it was continuously stirred until it began refluxing. Thezmixture-was maintained under'reflux conditions for about 30 minutes after which the pH was adjusted to about.5.5 'by the addition of Water was then removed from the mixture by azeotropic distillation for a period of from 2-3 hours. The remaining mixture was distilled flask at a rate of about-3 moles) were charged to a condenser. hydroxide 105 C. Thereafter, butanol was removed by vacuum distillation at 100 .mm. pressure to yield a vresinhaving from 65-70% total solids The resin was diluted with xylol to a-solids content of about 60% and'filtered using a filter aid. The resin thus obtained'did not have any pink or lavendercoloration.

Example 2 The entire procedure of Example 1 was repeated except that no nitrogen was used, the reaction mixture being exposed to air. The resin produced from monophenylmelamine made under these conditions was a light lavender color.

Example 3 In view of the observation that a wet cake of 2,4-diamino-6-chloro-s-triazine occludes an appreciable quantity of oxygen, the procedure of Example 1 was modified slightly to insure the exclusion of all oxygen from the reaction. T e 400 parts of water and 50.0 parts of 2,4-diamino-6-chloro-s-tr1azine were charged to the same reaction flask heated to reflux and refluxed for 10 minutes at a pressure of 100 mm. of Hg. As the vacuum was broken preparatory to charging the aniline, the system was thoroughly flushed with nitrogen to carefully exclude any air and the aniline the flask. The reaction heated to reflux temperature and maintained under reflux conditions for about 3 hours while dry nitrogen was continuously passed into the flask at a rate of about 3 liters per hour to maintain an inert atmosphere throughout the reaction period.

T he solution was filtered while hot and t e filtrate was cooled to 30 C. The filtrate was neutralized and the precipitated monophenylmelamine was recovered exactly as described in Example I and in comparable yield.

The resin produced with this monophenylmelamine according to the same formulation described in Example 1 had no objectionable pink or lavender coloration.

It is to be understood that this invention is not limited to the particular conditions given in the examples. For example, in addition to nitrogen, other gases which may period of 2-3 ered be used to prevent contact of the lengthens process time needlessly.

Formation of the aryl-substituted melamine occurs readily at temperatures from 50 C. upwards. Preferred the range from 95 to C., although higher temperatures requiring the use of pressure may be employed if desired. A minimum reaction ours is required to effect complete reaction and secure maximum yields.

Neutralization and precipitation of the monophenyl- 'melamme hydrochloride from solution can be accomto maintain it at The precipitated monophenylmelamine by any convenient method. Preferably, it is recovered by filtration or centrifugation and then washed and dried.

What is claimed is:

- of nitrogen.

can be recov-Z' conducting the reaction of 2,4-diamino-6-chloro-s-triazine and aniline under an atmosphere consisting of nitrogen.

' monophenylmelamine wherein 2,4-diamino-6-chloro-s-triazine and monophenylmelamine, the improvement which comprises refluxing the 2,4-diamino-6-chloro-s-triazine and water under vacuum to remove resulting degassed slurry the system with substantially pure nitrogen, and thereair, adding the aniline to the References Cited in the file of this patent UNITED STATES PATENTS Widmer Aug. 31, 1948 OTHER REFERENCES Walker et al.: J. Am. Pharm. Assoc., vol. 39, pages Banks: I. Am. Chem. Soc., vol. 66, pages 1127-1130 (1944).

Banks et al.:

J. Am. Chem. 500., vol. 66, pages 1771 

1. IN THE PROCESS FOR THE PRODUCTION OF MONOPHENYLMELAMINE WHEREIN 2,4-DIAMINO-6-CHLORO-S-TRAIZINE AND ANILINE ARE REACTED IN AQUEOUS MEDIUM AND THE MONOPHENYLMELAMINE HYDROCHLORIDE FORMED IS SUBSEQUENTLY NEUTRALIZED WITH AN ALKALI METAL HYDROXIDE TO OBTAIN THE MONOPHENYLMELAMINE, THE IMPROVEMENT WHICH COMPRISES CONDUCTING THE REACTION OF 2,4-DIAMINO-6-CHLORO-S-TRIAZINE AND ANILINE UNDER AN ATOMSPHERE OF AN INERT GAS CHOSEN FROM THE GROUP CONSISTING OF NITROGEN, CARBON DIOXIDE, HYDROGEN, ARGON, METHANE, ETHANE, AND HEXANE. 